EP0961931B1 - Method of standard-less phase analysis by means of a diffractogram - Google Patents

Method of standard-less phase analysis by means of a diffractogram Download PDF

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Publication number
EP0961931B1
EP0961931B1 EP98957075A EP98957075A EP0961931B1 EP 0961931 B1 EP0961931 B1 EP 0961931B1 EP 98957075 A EP98957075 A EP 98957075A EP 98957075 A EP98957075 A EP 98957075A EP 0961931 B1 EP0961931 B1 EP 0961931B1
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European Patent Office
Prior art keywords
substance
determined
mixture
diffraction
sample
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EP98957075A
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German (de)
English (en)
French (fr)
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EP0961931A1 (en
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Derk Reefman
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Malvern Panalytical BV
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Panalytical BV
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
    • G01N23/20016—Goniometers

Definitions

  • the invention relates to a method of determining the concentrations of the constituents in a mixture of substances, in which for each of the substances the set of associated diffraction reflections is identified in a radiation diffractogram of the mixture and the relative intensities of each set of diffraction reflections are determined.
  • phase is to be understood to mean a component of the mixture which causes own, characteristic diffraction reflections (also referred to as diffraction lines or lines for short) in the diffractogram.
  • a phase may be a component formed by a substance having a separate chemical composition, or a substance which does not deviate from another component of the mixture in respect of chemical composition but only in respect of crystalline appearance. Quantization of the various phases of a mixture, i.e.
  • the determination of the quantity of matter of the components in the mixture on the basis of a diffractogram of the mixture generally involves the problem that some information on the mixture should be available in advance so as to enable the quantization to be performed.
  • Existing methods of quantization can be split into two groups, i.e. the methods which utilize a standard and the methods which can be performed without a standard.
  • the diffractogram i.e. the positions of the reflections and also their absolute intensities
  • This data can be determined experimentally as well as theoretically, for example by means of computer simulation. In many cases, however, such data is not available, for example because the structure of several components of the mixture is not known and these components are not separately available either, as is some times the case for natural minerals.
  • a first drawback is that the reliability of the analysis result is strongly degraded when the absorption contrast becomes low. The latter is practically always the case for mineralogical and organic materials (notably pharmaceutical materials). Further drawbacks are that with this known method generally the effective absorption coefficient is unknown, that the effect of texture in the specimen may be high, and that n measurements must be performed for a sample containing n components.
  • the method according to the invention is characterized in that
  • the invention is based on the recognition of the fact that in the case of diffraction the total dispersive power per quantity of material can be predicted on theoretical grounds. This insight will be described in detail hereinafter.
  • the invention also offers the additional advantages that the effective absorption coefficient need not be known, that the texture in the sample practically has no effect on the result, and that a single measurement suffices also for a sample containing n components.
  • the relative power spectrum is determined from the measured relative intensities by extrapolation.
  • only one parameter of the extrapolation function need be determined in the process of adapting the theoretical variation to the known variation.
  • the extrapolation function of said extrapolation contains the Fourier transform of the electron density of the individual atoms of the relevant constituent. This function can be readily determined from known volumes of tables in which these electron densities are stated in the form of tables. Computer algorithms which are known per se are available so as to derive the Fourier transform thereof.
  • said extrapolation function contains a term which is dependent on the temperature of the relevant substance.
  • the adaptation of the function representing this total dispersive power becomes more accurate and easier. Such higher accuracy is achieved by addition of said temperature-dependent term.
  • the volume integral of the square of the electron density is determined from its chemical structural formula.
  • the structural formula instead of merely the general compositional formula, more information is obtained as regards the crystallographic structure of the substance to be analyzed.
  • a higher accuracy can be achieved in determining the volume integral of the square of the electron density, so a higher accuracy in determining the concentrations of the constituents of the mixture to be analyzed.
  • a known concentration of a known substance is added to the sample.
  • This method is suitable for those cases in which the mixture to be analyzed contains amorphous constituents.
  • the concentrations of the crystalline constituents of the mixture can then be determined by adding a known concentration of a known substance to the sample; the scale factor and the relative intensities of the diffraction lines of said known substance must then be known. This is again a case of standard-less analysis, because it does not require a standard of the phases to be analyzed in the mixture.
  • the above fundamental difficulty can be circumvented on the basis of the insight underlying the invention by making an estimate of the overall dispersive power on the basis of the diffraction reflections (lines) that can be observed.
  • the following approach is then used.
  • the starting point is the assumption that the overall appearance of the curve representing the mean variation of the intensity of the diffraction lines associated with all values of
  • the latter parameters can be determined, by extrapolation, from the observed diffraction lines and the chemical composition of the sample which is assumed to be known.
  • I i K . A . S . I i , rel . c
  • K is a constant which is dependent only on the diffractometer used
  • A is the absorption coefficient of the relevant substance
  • S is a scale factor which establishes the relationship between the observed relative intensity I i,rel of a line (i.e. the intensity of a line expressed in the intensity of another line, preferably that having the highest intensity) and the absolute intensity I i thereof
  • c is the concentration of the relevant phase in the mixture to be examined.
  • I i,rel of a phase are known from tables (or can be measured).
  • the mixture of phases to be analyzed consists of only two phases D and E, and that the mixture does not contain amorphous constituents.
  • the following procedure can be used to determine the scale factor S of a phase.
  • the total intensity that can be taken into account for diffraction is found using the square of the Fourier transform of the charge distribution of the electron clouds of the substance subject to diffraction present in the relevant volume V.
  • the still unknown power spectrum can be obtained by making an extrapolation of the intensity spectrum according to the invention in such a manner that a suitable approximation of the power spectrum is obtained.
  • the known assumption is made that I i ( G ) decreases with
  • can be derived therefrom.
  • a suitable determination of the as yet unknown left term of the expression (7) can be achieved according to the invention by using a method which is known per se. This method implies that the integral in the left-hand term is determined from the known charge density distributions of the constituent electron clouds in the crystallographic unity cell.
  • a weighted contribution of the individual atoms in the compound is used, the weight factor being derived from the chemical compositional formula (so, for example, in CaCl 2 , Cl is weighted twice as much as Ca).
  • the scale factor S can be determined for each of the phases in the mixture.
  • concentrations C D and C E in the expression (2) can thus be solved.
  • the scale factor S and the various I i,rel values of this substance must then be known.
  • the factor K.A can be determined from the expression (1).
  • the scale factor S can be determined for the unknown phase, after which the concentration of the unknown phase can be determined by means of the expression (1).
  • Fig. 1 shows an X-ray diffraction device in which a goniometer 4 is mounted on a frame 2.
  • the goniometer 4 is provided with a scale graduation 6 for measuring the angular rotation of the X-ray source 7 , being mounted thereon, and of the detector device 9 which is also mounted thereon.
  • the goniometer moreover, is provided with a sample holder 8 on which a sample 10 is arranged.
  • a scale graduation 12 is provided.
  • the X-ray source 7 includes a holder 12 for an X-ray tube (not shown in the Figure) which is secured in the holder by way of a fixing ring 20.
  • the X-ray tube includes a high-voltage connector 16 via which the high voltage and the filament current for the X-ray tube are supplied via the high voltage cable 18.
  • Supply and discharge ducts 22 and 24 for the cooling water of the X-ray tube are provided at the same side of the X-ray tube.
  • the tube holder 12 also comprises an exit window for X-rays 14 and a unit 16 for parallelization of the X-ray beam (a Soller slit).
  • the detector device 9 consists of a holder 26 for a Soller slit, a holder 28 for a monochromator crystal, and a detector 30.
  • the X-ray source as well as the detector is rotatable about the sample, as shown in the Figure, it is not necessary for the sample to be arranged so as to be rotatable. However, it is alternatively possible to mount the X-ray source so as to be stationary, as may sometimes be necessary in the case of voluminous and heavy X-ray sources. In that case the specimen holder as well as the detector should be rotatable.
  • the X-ray diffraction device as shown in Fig. 1 also includes a processing device for processing the various measured data.
  • the processing device consists of a central processing unit 32 whereto a memory unit 36 and a monitor 34 for the presentation of the various data and for the display of the measured and calculated result are connected. It will be evident that the memory unit 36 need not be separately constructed and that it may form part of the central processing unit 32.
  • the X-ray source 7 , the detector device 9 and the specimen holder 8, mounted on the goniometer 4 are all provided with a unit (not shown) for determining the angular position of the relevant element with respect to the scale graduation of the goniometer.
  • a signal representing this angular position is applied, via connection leads 38-1, 38-2 and 38-3, to the central processing unit 32.
  • the memory unit 36 stores the data required to carry out the analysis as will be described in detail with reference to Fig. 2 .
  • a diffractogram of the mixture to be quantified is formed in known manner, i.e. the intensity and the angular position of the various diffraction lines are determined by traversing the entire angular range 0 ⁇ ⁇ ⁇ 2 ⁇ .
  • Fig. 2 shows a flow chart illustrating the various steps carried out to determine the concentrations of the constituents of the mixture to be quantified from the X-ray diffractogram formed. It is assumed that a diffractogram of a mixture to be quantified, consisting of a number of phases, is available. The diffractogram consists of a number of diffraction reflections or diffraction lines, each of which has its own intensity. The relative intensity I i,rel of each of these diffraction lines is determined (40), i.e. the intensity of a diffraction line expressed in the intensity of the diffraction lines of the total diffractogram which have the highest intensity.
  • the total diffractogram consists of a number of completely or partly overlapping sets of diffraction lines, each time one set being associated with a phase of the mixture to be quantified. Because, generally speaking, the diffractogram of each of the phases (i.e. the values of I i,rel and the location of the diffraction lines) is known (for example, from tables or by measurement performed on a pure phase), the total diffractogram can be split into the separate sets of diffractograms, each of which is associated with one of the phases (42).
  • the atomic number Z i is used as input and the charge density ⁇ i ( r ) is obtained as a function of the position vector r . Because the result is spherical symmetrical, it may be simply stated that ⁇ i is obtained as a function of r. According to this Hartree-Fock method the volume of each of the atoms i, as required subsequently, is also obtained. According to the alternative method of determining the charge density as a function of r, use is made of generally known tables in which these values are stated in tabular form. The array of values (i.e.
  • ⁇ as a function of r) obtained by means of one of the described methods can then be stored in the memory 36 wherefrom they can be fetched as required for processing by the computer program.
  • the block 44 in the flow chart represents the acquisition of the charge density ⁇ i ( r ) as a function of the position vector r .
  • ⁇ i as a function of r is known for each of the atoms in the chemical compositional formula
  • a suitable approximation of the variable ⁇ 2 ( r ) can be obtained for the total number of atoms in the chemical compositional formula by summing the values ⁇ i 2 ( r ) for each of the atoms, see block 46.
  • the N volumes V i,at of the N individual atoms, already obtained by means of the Hartree-Fock method are summed, so that a suitable approximation of the volume V e of the unity cell is obtained, see block 48.
  • ⁇ as a function of r stored in the memory 36, is then used for the numerical execution of the integration.
  • the integration implies that the variable ⁇ 2 ( r ) is continuously multiplied by the infinitely small volume of a shell of a sphere 4 ⁇ r 2 dr and the products thus obtained are accumulated.
  • This procedure is symbolically represented in the block 50.
  • the left term of the expression (7) is known and available.
  • the scale value S is determined for each phase of the mixture to be quantified.
  • the Fourier transform FT[ ⁇ ( r )] is determined.
  • the variables ⁇ ( r ) were already known: see the blocks 44 and 46 in which these variables have been obtained as an intermediate result yielded by the summing over the atoms of the chemical compositional formula.
  • the execution of the Fourier transformation of these variables (block 52) is a generally known method which need not be elaborated herein. This transformation yields an array of values of FT[ ⁇ ( r )] as a function of
  • the left term of the expression (8) is known, because I(
  • the function values in this array are a function of
  • 2 ) is not known, but in this factor the value of B is determined by adapting this unknown function to the other known variables in this expression, see block 54.
  • the procedure used to find the scale value S is as follows. First the series of known intensities I i,rel is assumed to be a curve as a function
  • G, the initial value of G being set to G 0 and the final value (so of the last diffraction line measured) to G 1 . After that it is assumed that the surface area below said curve, between G 0 and G 1 , is equal to a constant K times the sum of the measured values I i,rel ; block 56.
  • the concentrations C D , C E etc. of the phases can be determined by means of these known scale values S D , S E etc., see block 64.
  • a known concentration of a known reference substance must be added to the sample, for example 0.1 % Al 2 O 3 .
  • the scale factor S and the various values of I i,rel of this substance must be known.
  • the factor K.A in the expression (1) can be determined and, using the expression (7), the scale factor S can be determined for the unknown phases, after which the concentration of the unknown phase can be determined by means of the expression (1), see block 66.

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EP98957075A 1997-12-22 1998-12-14 Method of standard-less phase analysis by means of a diffractogram Expired - Lifetime EP0961931B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98957075A EP0961931B1 (en) 1997-12-22 1998-12-14 Method of standard-less phase analysis by means of a diffractogram

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP97204064 1997-12-22
EP97204064 1997-12-22
EP98957075A EP0961931B1 (en) 1997-12-22 1998-12-14 Method of standard-less phase analysis by means of a diffractogram
PCT/IB1998/002016 WO1999032880A1 (en) 1997-12-22 1998-12-14 Method of standard-less phase analysis by means of a diffractogram

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EP0961931A1 EP0961931A1 (en) 1999-12-08
EP0961931B1 true EP0961931B1 (en) 2008-04-23

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EP (1) EP0961931B1 (ja)
JP (1) JP4115542B2 (ja)
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WO (1) WO1999032880A1 (ja)

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JP3950239B2 (ja) * 1998-09-28 2007-07-25 株式会社リガク Ｘ線装置
JP3722454B2 (ja) * 1998-11-02 2005-11-30 株式会社リガク ソーラスリット及びその製造方法
US6678347B1 (en) 2002-07-26 2004-01-13 Hypernex, Inc. Method and apparatus for quantitative phase analysis of textured polycrystalline materials
US7127037B2 (en) * 2002-07-26 2006-10-24 Bede Scientific Instruments Ltd. Soller slit using low density materials
JP5381925B2 (ja) * 2010-07-27 2014-01-08 新日鐵住金株式会社 酸化物の構造評価方法
CN108169255B (zh) * 2016-12-07 2020-06-30 同方威视技术股份有限公司 多能谱x射线成像系统和用于利用多能谱x射线成像系统对待测物品进行物质识别的方法

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DK131955C (da) * 1973-10-09 1976-02-23 I Leunbach Fremgangsmade og anleg til bestemmelse af elektrontetheden i et delvolumen af et legeme
US4592082A (en) * 1984-08-10 1986-05-27 The United States Of America As Represented By The United States Department Of Energy Quantitative determination of mineral composition by powder X-ray diffraction
JP2976305B2 (ja) * 1990-01-30 1999-11-10 日本航空電子工業株式会社 アモルファス監視装置
US4991191A (en) * 1990-02-05 1991-02-05 The Regents Of The University Of Minnesota Quantitative analysis of the active table ingredient by power x-ray diffractometry
DE4331317A1 (de) * 1993-09-15 1995-03-16 Philips Patentverwaltung Untersuchungsverfahren zur Auswertung ortsabhängiger Spektren
JPH09178675A (ja) * 1995-12-27 1997-07-11 Kawasaki Steel Corp 深さ方向集合組織の測定方法

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DE69839390T2 (de) 2009-05-20
WO1999032880A1 (en) 1999-07-01
JP4115542B2 (ja) 2008-07-09
DE69839390D1 (de) 2008-06-05
JP2001513902A (ja) 2001-09-04
US6108401A (en) 2000-08-22
EP0961931A1 (en) 1999-12-08

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